CN108047686A - Expanded moldings - Google Patents

Expanded moldings Download PDF

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Publication number
CN108047686A
CN108047686A CN201810021542.5A CN201810021542A CN108047686A CN 108047686 A CN108047686 A CN 108047686A CN 201810021542 A CN201810021542 A CN 201810021542A CN 108047686 A CN108047686 A CN 108047686A
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Prior art keywords
dihydroxy compounds
structural unit
copolycarbonate
formula
expanded moldings
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CN201810021542.5A
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CN108047686B (en
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高岛彻
山冈克史
石川健
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Mitsubishi Chemical Corp
Mitsubishi Kasei Corp
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Mitsubishi Kasei Corp
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04Aromatic polycarbonates
    • C08G64/06Aromatic polycarbonates not containing aliphatic unsaturation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34Auxiliary operations
    • B29C44/58Moulds
    • B29C44/586Moulds with a cavity increasing in size during foaming
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02Aliphatic polycarbonates
    • C08G64/0208Aliphatic polycarbonates saturated
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/122Hydrogen, oxygen, CO2, nitrogen or noble gases
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2069/00Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037Other properties
    • B29K2995/0063Density
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08J2467/03Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the hydroxy and the carboxyl groups directly linked to aromatic rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation

Abstract

The present invention provides a kind of easy to manufacture, light weight and the excellent formed body such as mechanical property, which made containing isobide for obtained from the Copolycarbonate foaming of raw material.Expanded moldings of the present invention include Copolycarbonate, and its glass transition temperature (Tg) is less than 145 DEG C, the Copolycarbonate has the structural unit of the dihydroxy compounds represented from following formula (1) and the structural unit from other dihydroxy compounds.

Description

Expanded moldings
The application is the applying date for August in 2012 30 days, Application No. 201280041682.X, entitled " foaming The divisional application of the application of formed body ".
Technical field
The present invention relates to the formed bodys that Copolycarbonate is made to foam and is formed.
Background technology
Polycarbonate resin is manufactured usually using the raw material derived from petroleum resources.But in recent years, it is faced with oil money The danger of source exhaustion, it is desirable that provide using polycarbonate resin obtained from the raw material obtained as biomass resources such as plants.Separately Outside, the increase due to CO2 emissions, accumulation caused by global warming can bring climate change etc., also requirement exploitation is Neutral carbon, polycarbonate resin using the monomer from plant as raw material can also be kept by making to carry out waste treatment after use.
Due to case above, it is proposed that the isobide for example used as the monomer from plant, and by with carbonic acid The ester exchange reaction of diphenyl ester obtains polycarbonate resin (for example, referring to patent document 1).Further, since contain different sorb Alcohol is excellent and with heat resistance for the mechanical property of the polycarbonate resin of raw material, therefore proposes and use it for automobile component Wait industrial materials purposes (for example, referring to patent document 2).
On the other hand, formed body (expanded moldings) is light weight, thermal insulation and impact obtained from making polymer foaming The excellent structure of absorbability can efficiently use its characteristic and a variety of materials use is made.Wherein, disclosed in patent document 3 The polycarbonate resin (isobide homopolymer) using isobide as raw material is subjected to foaming under given conditions and Obtained foam molded product.In addition, the comparison of the polycarbonate resin using dissolved carbon dioxide is disclosed in patent document 4 Example.
Prior art literature
Patent document
Patent document 1:No. 1,079,686 specifications of British Patent No.
Patent document 2:Japanese Unexamined Patent Publication 2009-74031 publications
Patent document 3:Japanese Unexamined Patent Publication 2009-964 publications
Patent document 4:Japanese Unexamined Patent Publication 2002-192549 publications
The content of the invention
Problems to be solved by the invention
For the expanded moldings containing isobide for the polycarbonate resin of raw material, do not carry out research substantially and open Hair, with regard to known to the inventors of the present invention, the expanded moldings of its homopolymer are only proposed in patent document 3.But patent document 3 In the foam performance of isobide homopolymer may not be good.Although it in addition, is disclosed in patent document 4 using dissolving dioxy Change the example of the polycarbonate resin of carbon, but the example is comparative example, it follows that the foaminess of previous polycarbonate resin It can may not be good.
If being capable of providing the expanded moldings for the polycarbonate resin of raw material containing isobide, purposes can Expand, it is desirable that easy to manufacture and the expanded moldings with superperformance.
It is an object of the present invention to provide the formed body that a kind of easy to manufacture, light weight and mechanical property etc. are excellent, this into Type body is made containing isobide for obtained from the Copolycarbonate foaming of raw material.Solution to the problem
In order to solve the above problems, the inventors of the present invention be repeated further investigation it turns out that, have from different mountain The structural unit of pears alcohol and from other dihydroxy compounds, such as cyclohexanedimethanol class, Tricyclodecane Dimethanol class or oneself The structural unit of glycols, and glass transition temperature has excellent foaming in the Copolycarbonate of a certain particular range Performance can form light weight and the high formed body of intensity.The present invention is namely based on above-mentioned discovery and completes.
That is, purport of the invention is as described below.
[1] a kind of expanded moldings, it includes Copolycarbonate, and glass transition temperature (Tg) is less than 145 DEG C, The Copolycarbonate has the structural unit of the dihydroxy compounds represented from following formula (1) and from other dihydroxy The structural unit of based compound.
[chemical formula 1]
[2] expanded moldings described in above-mentioned [1], wherein, the structural unit from other dihydroxy compounds is to be selected from At least one of following structural units structural unit:
The structural unit of the dihydroxy compounds represented from following formula (2),
HO-R1-OH (2)
(in formula (2), R1Represent the substituted or unsubstituted ring alkylidene of carbon number 4~20);
The structural unit of the dihydroxy compounds represented from following formula (3),
HO-CH2-R2-CH2-OH (3)
(in formula (3), R2Represent the substituted or unsubstituted ring alkylidene of carbon number 4~20);
The structural unit of the dihydroxy compounds represented from following formula (4),
H-(O-R3)p-OH (4)
(in formula (4), R3Represent the substituted or unsubstituted alkylidene of carbon number 2~10, p is 2~50 integer);With And
The structural unit of the dihydroxy compounds represented from following formula (5),
HO-R4-OH (5)
(in formula (5), R4Represent the substituted or unsubstituted alkylidene of carbon number 2~20 or substituted or unsubstituted Group with acetal ring).
[3] expanded moldings described in above-mentioned [1] or [2], wherein, the structural unit from other dihydroxy compounds is Selected from least one of cyclohexanedimethanol class, Tricyclodecane Dimethanol class and hexylene glycol class structural unit.
[4] expanded moldings any one of above-mentioned [1]~[3], wherein, compared with institute in Copolycarbonate What is contained all is from the structural unit of dihydroxy compounds, the ratio of the structural unit of the dihydroxy compounds represented from formula (1) Example is 30 moles of more than % and 99 mole of below %.
[5] expanded moldings any one of above-mentioned [1]~[4] are will to meet the resin groups of following characters (1) Obtained from closing object progress foaming,
(1) carbon dioxide at 200 DEG C is 2.5 × 10 compared with the Henry's constant of resin combination-3~4.0 × 10- 3The resin combination of g (carbon dioxide)/g (resin combination) MPa.
[6] expanded moldings any one of above-mentioned [1]~[5], expansion ratio are 1.1 times or more and 100 times Following scope.
[7] expanded moldings described in above-mentioned [5] or [6] are using foaming agent, by expanding with die cavity (Cavity) The foam-injection opened makes obtained from the resin combination foaming.
[8] expanded moldings described in above-mentioned [7], wherein, foaming agent is inorganic gas.
[9] expanded moldings described in above-mentioned [8], wherein, inorganic gas is nitrogen or carbon dioxide.
[10] expanded moldings any one of above-mentioned [7]~[9], wherein, the cavity volume phase after die cavity expansion It is the scope more than 1.1 times and less than 20 times that cavity volume when completing is filled for resin combination.The effect of invention
According to the present invention, can obtain that expansion ratio is high, impact resistance is good, i.e. particularly light weight, excellent strength, The excellent expanded moldings of tensile modulus of elasticity.
Specific embodiment
Hereinafter, the present invention is described in detail.It should be noted that the present invention is not limited to implementations described below Mode can carry out various modifications within the scope of its subject matter to implement.
In addition, in the present specification, " mass parts " are synonymous with " parts by weight ".
First, the Copolycarbonate used in the present invention is illustrated, then, to resin combination, be foamed into Type method, purposes of expanded moldings (following, to be also recorded as " formed body ") etc. illustrate.
[1] Copolycarbonate
Copolycarbonate in the present invention is with the structure list from the dihydroxy compounds shown in following formula (1) Member and the structural unit from other dihydroxy compounds and the copolymer with specific glass transition temperature, can be with It is manufactured by using following dihydroxy compounds for raw material.
[chemical formula 2]
Dihydroxy compounds > shown in < formulas (1)
As the dihydroxy compounds (following, it is sometimes abbreviated as " compounds of formula (1) ") shown in above-mentioned formula (1), For example, isobide, different mannide, different iditol there are stereoisomer relation.These compounds point It is not obtained by D-Glucose, D-MANNOSE, L- idoses.For example, in the case of isosorbide, can to D-Glucose into After row hydrogenation, it is dehydrated and is obtained by using acid catalyst.
These dihydroxy compounds can be used alone, and can also be used in combination of two or more.These dihydroxies It closes in object, from the aspect of the easy degree, optical characteristics, mouldability for obtaining and manufacturing, most preferably by being deposited as resourceful And can easily obtain various starch manufacture sorbierite through isobide obtained from dehydrating condensation.
The other dihydroxy compounds > of <
As other dihydroxy compounds, as long as the change of usually used polymerization and above-mentioned formula (1) can be passed through The dihydroxy compounds that object forms Copolycarbonate together is closed, then is not particularly limited, preferably for example selected from following formula (2) At least any one compound in dihydroxy compounds shown in~(5).It should be noted that in following, various groups Carbon number refers to for the carbon number of the substituent group to be also included within interior total carbon original in the case where the group has substituent group Subnumber.
HO-R1-OH (2)
(in formula (2), R1Represent the substituted or unsubstituted ring alkylidene of carbon number 4~20.)
HO-CH2-R2-CH2-OH (3)
(in formula (3), R2Represent the substituted or unsubstituted ring alkylidene of carbon number 4~20.)
H-(O-R3)p-OH (4)
(in formula (4), R3Represent the substituted or unsubstituted alkylidene of carbon number 2~10, p is 2~50 integer.)
HO-R4-OH (5)
(in formula (5), R4Represent the substituted or unsubstituted alkylidene of carbon number 2~20 or substituted or unsubstituted Group with acetal ring.)
Hereinafter, the dihydroxy compounds shown in above-mentioned formula (2)~(5) is more specifically illustrated.
Dihydroxy compounds > shown in < formulas (2)
Dihydroxy compounds (following, it is sometimes abbreviated as " compounds of formula (2) ") shown in formula (2) is former with carbon The substituted or unsubstituted ring alkylidene of subnumber 4~20, preferably carbon number 4~18 is as R1Ester ring type dihydroxy chemical combination Object.Wherein, R1In the case of with substituent group, as the substituent, the substitution or unsubstituted of carbon number 1~12 can be enumerated Alkyl, the alkyl have substituent group in the case of, as the substituent, the alkane such as methoxyl group, ethyoxyl, propoxyl group can be enumerated Aryl such as oxygroup, phenyl, naphthalene etc..
The dihydroxy compounds is by that with ring structure, can improve obtained Copolycarbonate shaping when institute The toughness of obtained molded product.
As R1Ring alkylidene, as long as the alkyl with ring structure, then be not particularly limited or with bridge The bridged linkage of head carbon atom.From the easy to manufacture of dihydroxy compounds and from the viewpoint of impurity level being reduced, above-mentioned formula (2) compound of the dihydroxy compounds preferably comprising 5 ring structures or 6 ring structures shown in, i.e. R1To substitute or not taking The ring pentylidene in generation or the dihydroxy compounds of substituted or unsubstituted cyclohexylene.If such dihydroxy chemical combination Object, then can be by improving the heat resistance of obtained Copolycarbonate containing 5 ring structures or 6 ring structures.This 6 Ring structure can be fixed as chair form or boat form by covalent bond.
Wherein, the compound of above-mentioned formula (2) is preferably R1The various isomers represented with following formula (7).Wherein, formula (7) In R11Represent the substituted or unsubstituted alkyl of hydrogen atom or carbon number 1~12.R11For the carbon atom with substituent group In the case of the alkyl of number 1~12, as the substituent, can enumerate the alkoxies such as methoxyl group, ethyoxyl, propoxyl group, phenyl, Aryl such as naphthalene etc..
[chemical formula 3]
As the compound of above-mentioned formula (2), more specifically, it can be cited for example that tetramethylcyclobutanediol, 1,2- rings penta 2 Alcohol, 1,3- rings pentanediol, 1,2- cyclohexanediols, 1,3- cyclohexanediols, 1,4- cyclohexanediols, 2- methyl-1s, 4- cyclohexanediols, three Cyclodecane glycols, pentacyclopentadecandimethanol glycols etc., but it is not limited to these.
According to the requirement performance of obtained Copolycarbonate, the compound of above-mentioned formula (2) can be used alone one Kind, it can also be used in combination of two or more.
Dihydroxy compounds > shown in < formulas (3)
Dihydroxy compounds (following, it is sometimes abbreviated as " compounds of formula (3) ") shown in above-mentioned formula (3) is that have The substituted or unsubstituted ring alkylidene of carbon number 4~20, preferably carbon number 3~18 is as R2Ester ring type dihydroxy Close object.Wherein, R2In the case of with substituent group, as the substituent, the substitution of carbon number 1~12 can be enumerated or do not taken The alkyl in generation in the case that the alkyl has substituent group, as the substituent, can enumerate methoxyl group, ethyoxyl, propoxyl group etc. Aryl such as alkoxy, phenyl, naphthalene etc..
The dihydroxy compounds is by that with ring structure, can improve obtained Copolycarbonate shaping when institute The toughness of obtained molded product.
As R2Ring alkylidene, as long as the alkyl with ring structure, then be not particularly limited or with bridge The bridged linkage of head carbon atom.From the easy to manufacture of dihydroxy compounds and from the viewpoint of impurity level being reduced, above-mentioned formula (3) compound of the dihydroxy compounds preferably comprising 5 ring structures or 6 ring structures shown in, i.e. R2To substitute or not taking The ring pentylidene in generation or the dihydroxy compounds of substituted or unsubstituted cyclohexylene.If such dihydroxy chemical combination Object, then can be by improving the heat resistance of obtained Copolycarbonate containing 5 ring structures or 6 ring structures.This 6 Ring structure can be fixed as chair form or boat form by covalent bond.The compound of above-mentioned formula (3) is preferably R2With above-mentioned formula (7) table The various isomers shown.
As the compound of above-mentioned formula (3), more specifically, the pentamethylene dimethanols such as 1,3- pentamethylene dimethanols can be enumerated Cyclohexanedimethanols class, the 3,8- such as class, 1,2- cyclohexanedimethanols, 1,3- cyclohexanedimethanols, 1,4 cyclohexane dimethanol are double (methylol) tricyclic [5.2.1.02.6] decane, double (methylol) tricyclic [5.2.1.0 of 3,9-2.6] decane, 4,8- double (methylol) Tricyclic [5.2.1.02.6] decane, double (methylol) tricyclic [5.2.1.0 of 4,9-2.6] the Tricyclodecane Dimethanols class such as decane, but simultaneously It is not limited to these.
According to the requirement performance of obtained Copolycarbonate, the compound of above-mentioned formula (3) can be used alone one Kind, it can also be used in combination of two or more.
That is, due in manufacture, above-mentioned dihydroxy compounds is obtained in the form of the mixture of isomers sometimes, this When, it can be used directly in the form of isomer mixture.It is, for example, possible to use 3,8- double (methylol) tricyclics [5.2.1.02.6] decane, double (methylol) tricyclic [5.2.1.0 of 3,9-2.6] decane, double (methylol) tricyclics of 4,8- [5.2.1.02.6] double (methylol) tricyclic [5.2.1.0 of decane and 4,9-2.6] decane mixture.
In the specific example of the compound of above-mentioned formula (3), particularly preferred cyclohexanedimethanol class, easiness from acquisition, From the viewpoint of the easiness of operation is such, preferably 1,4-CHDM, 1,3-CHDM, 1,2- hexamethylenes two Methanol.
Dihydroxy compounds > shown in < formulas (4)
Dihydroxy compounds (following, it is sometimes abbreviated as " compounds of formula (4) ") shown in above-mentioned formula (4) is that have The substituted or unsubstituted alkylidene of carbon number 2~10, preferably carbon number 2~5 is as R3Compound.P for 2~50, Preferably 2~30, it is more preferably 2~15 integer.
As the compound of above-mentioned formula (4), can specifically enumerate:Diethylene glycol, triethylene glycol, polyethylene glycol (molecular weight 150~4000) etc., but it is not limited to these.As the compound of above-mentioned formula (4), the poly- second of preferred molecular weight 300~2000 Glycol, wherein the polyethylene glycol of particularly preferred molecular weight 600~1500.
According to the requirement performance of obtained Copolycarbonate, the compound of above-mentioned formula (4) can be used alone one Kind, it can also be used in combination of two or more.
Dihydroxy compounds > shown in < formulas (5)
Dihydroxy compounds (following, it is sometimes abbreviated as " compounds of formula (5) ") shown in above-mentioned formula (5) is that have The substituted or unsubstituted alkylidene of carbon number 2~20, preferably carbon number 2~10 is substituted or unsubstituted with contracting The group of aldehyde ring is as R4Dihydroxy compounds.R4The substituted base of alkylene group in the case of, as the substituent, can be with Enumerate the alkyl of carbon number 1~5.In addition, R4The group with acetal ring with substituent group in the case of, as the substitution Base can enumerate the alkyl of carbon number 1~3.
In the compound of above-mentioned formula (5), as R4For the dihydroxy of the substituted or unsubstituted alkylidene of carbon number 2~20 Based compound, it can be cited for example that:The propandiolses such as 1,3- propylene glycol, 1,2- propylene glycol, 1,4- butanediols, 1,3 butylene glycol etc. Hexylene glycols classes such as the pentanediols such as butanediol category, 1,5-PD class, 1,6- hexylene glycols etc., but it is not limited to these.It is above-mentioned to work as In, preferred hexylene glycol class.
On the other hand, as R4For the dihydroxy compounds of the substituted or unsubstituted group with acetal ring, no spy It does not limit, wherein, preferably following formula (8), the dihydroxy compounds with spirane structure shown in formula (9) are particularly preferably following The dihydroxy compounds with multiple ring structures shown in formula (8).
[chemical formula 4]
In these dihydroxy compounds, reactivity when easiness from acquisition, the easiness of operation, polymerization is high, gained From the viewpoint of the form and aspect of the Copolycarbonate arrived, preferably 1,3-PD, 1,6- hexylene glycols.In addition, from heat resistance Viewpoint considers, preferably has the dihydroxy compounds class of the group comprising acetal ring, the tool represented by particularly preferred above-mentioned formula (8) There is the dihydroxy compounds of multiple ring structures.
According to the requirement performance of obtained Copolycarbonate, above-mentioned formula (5) compound represented can individually make With one kind, can also be used in combination of two or more.
Dihydroxy compounds > beyond < formulas (1)~(5) compound represented
For the Copolycarbonate of the present invention, the structure list of the compound except coming from above-mentioned formula (1)~(5) Beyond member, the structural unit of the dihydroxy compounds beyond the compound from above-mentioned formula (1)~(5) can also be contained.
As the dihydroxy compounds beyond the compound of formula (1)~(5), it can be cited for example that bisphenols etc..
As bisphenols, it can be cited for example that:Double (4- hydroxy phenyls) propane (=bisphenol-A) of 2,2-, double (the 4- hydroxyls of 2,2- Base -3,5- 3,5-dimethylphenyls) propane, double (4- hydroxyl -3,5- diethyl phenyls) propane of 2,2-, double (the 4- hydroxyls-(3,5- of 2,2- Diphenyl) phenyl) propane, double (4- hydroxyl -3,5- dibromo phenyls) propane of 2,2-, double (4- hydroxy phenyls) pentanes of 2,2-, 2,4 ' - Double (the 4- hydroxy benzenes of dihydroxydiphenyl methane, double (4- hydroxy phenyls) methane, double (4- hydroxyl -5- nitrobenzophenones) methane, 1,1- Base) ethane, 3,3- double (4- hydroxy phenyls) pentane, 1,1-bis(4-hydroxyphenyl)-cyclohexane, double (4- hydroxy phenyls) sulfones, 2, 4 '-dihydroxy-diphenyl sulfone, double (4- hydroxy phenyls) thioethers, 4,4 '-dihydroxydiphenyl ether, 4,4 '-dihydroxy -3,3 '-two Chlorodiphenyl base ether, 4,4 '-dihydroxy -2,5- diethoxy diphenyl ethers etc..
According to the requirement performance of obtained Copolycarbonate, the dihydroxy beyond the compound of above-mentioned formula (1)~(5) Based compound can be used alone, and can also be used in combination of two or more.
As the structural unit from other dihydroxy compounds in the Copolycarbonate of the present invention, preferably select Arbitrary structures unit from cyclohexanedimethanol class, Tricyclodecane Dimethanol class and hexylene glycol class.
The content ratio > of structural units of the < from dihydroxy compounds
Structural unit from the dihydroxy compounds shown in formula (1) is compared with from the complete of composition Copolycarbonate The ratio of the structural unit of portion's dihydroxy compounds is not particularly limited, and is usually 30 moles of more than %, is preferably 40 moles of % Above, be more preferably 50 moles of more than %, in addition, usually 99 moles of below %, be preferably 95 moles of below %, more preferably 90 moles of below %.
If the structural unit from the dihydroxy compounds shown in formula (1) is compared with from composition Copolycarbonate Whole dihydroxy compounds structural unit ratio be less than above range, then plant origin degree decline, in addition, vitrifying turn Temperature declines, it may not be possible to obtain the heat resistance of needs.In addition, if the knot from the dihydroxy compounds shown in formula (1) Structure unit is more than above-mentioned compared with the ratio of the structural unit from the whole dihydroxy compounds for forming Copolycarbonate Scope, then impact resistance decline, in addition, gas solubility is small, when foaming, possibly can not obtain sufficient light weight effect.
The physicochemical properties > of < Copolycarbonates
Wherein, Copolycarbonate of the invention is characterized in that, glass transition temperature is less than 145 DEG C.
For glass transition temperature (Tg), be preferably less than 140 DEG C as its upper limit, be more preferably 135 DEG C with Under, particularly preferably less than 130 DEG C, in addition, as its lower limit, be usually more than 40 DEG C, preferably 50 DEG C or more, be more preferably 60 DEG C or more, further preferably 70 DEG C or more.
If glass transition temperature is excessively high, there is the tendency that higher temperature is needed when carrying out foaming, in addition, Gas is small to the solubility of polymer, and possibly high expansion ratio can not be obtained when carrying out foaming.In addition, if glass It is too low to change transition temperature, then the heat resistance possible deviation of expanded moldings.
Other physicochemical properties beyond glass transition temperature (Tg) are not particularly limited, but preferably make to have following The Copolycarbonate of property foams that formed body is made.
First, the degree of polymerization of Copolycarbonate represents preferably more than 0.40dl/g with reduced viscosity, is more preferably More than 0.40dl/g, and the usually degree of polymerization of below 2.00dl/g, preferably below 1.60dl/g, the reduced viscosity is to make With phenol and the mass ratio 1 of 1,1,2,2- tetrachloroethanes:1 mixed solution is as solvent, by the accurate adjustment of makrolon concentration For 1.00g/dl, measured at 30.0 DEG C ± 0.1 DEG C of temperature.The extremely low Copolycarbonate of the reduced viscosity is being sent out Mechanical strength when soaking type dies down, in addition, if reduced viscosity is excessive, then there is mobility when being molded and is easily reduced Tendency.
In addition, Copolycarbonate although obtains single vitrifying when carrying out differential scanning calorimetry measure (DSC) Transition temperature, but the dihydroxy compounds when being manufactured shown in adjustment type (1) and other dihydroxy compounds can be passed through Species and proportioning obtain the polymer with arbitrary glass transition temperature.
In addition, 5% hot loss of weight temperature is preferably 340 DEG C or more, more preferably 345 DEG C or more.5% hot loss of weight temperature is got over Height, thermal stability become higher, and can tolerate the use under at higher temperature.Further, since manufacture temperature can also be improved, during manufacture Control range it is wider, therefore manufacture become easy.5% hot loss of weight temperature is lower, and thermal stability is lower, it is difficult in high temperature Lower use.In addition, control permissible range during manufacture narrows, it becomes difficult to make.Therefore, the upper limit of 5% hot loss of weight temperature does not have It is particularly limited to, it is the higher the better, the decomposition temperature of copolymer is limited to thereon.
In addition, Izod impact strength is preferably 30J/m2More than.Izod impact strength is bigger, and the intensity of formed body is got over It is to become higher, is more not easy to be destroyed, therefore its upper limit is not particularly limited.
In addition, gas of the Copolycarbonate of the present invention preferably at 110 DEG C beyond the phenol component of per unit area Body yield (hereinafter sometimes referred to simply as " gas generated ") is 5ng/cm2Hereinafter, in addition, more preferably from shown in formula (1) The gas generated of dihydroxy compounds beyond dihydroxy compounds is 0.5ng/cm2Below.This is gas generated fewer, then It can more be used to need the purposes for avoiding generating the influence of gas, such as the purposes of the electronic units such as semiconductor, building certainly Framework of interior material purposes, household appliances etc. etc..
It should be noted that 5% hot loss of weight temperature of Copolycarbonate, Izod impact strength, gas generated The specific as be described hereinafter implementation item of assay method shown in.
In the Copolycarbonate of the present invention, preferably there is at least two makrolon in above-mentioned physical property simultaneously Copolymer, such as it is 30J/m that glass transition temperature (Tg), which is less than 145 DEG C and Izod impact strength,2Above makrolon Copolymer, in addition, more preferably having the Copolycarbonate of other physical property simultaneously.If glass transition temperature is 145 DEG C More than, then when carrying out foaming in the presence of the tendency for needing higher temperature, in addition, gas solubility is small, when foaming, can It can be difficult to obtain high expansion ratio.In addition, if Izod impact strength is less than 30J/m2, then the intensity of expanded moldings can It can reduce.
The Copolycarbonate of the present invention can be manufactured using usually used polymerization, which can be with It is to have used the arbitrary methods such as solution polymerization process, the melt phase polycondensation reacted with carbonic diester carbonic acid of phosgene.More specifically For, dihydroxy compounds, the above-mentioned other dihydroxy shown in above-mentioned formula (1) are preferably for example made in the presence of polymerization catalyst Compound (any compound in the compound selected from formula (2)~(5)) and dihydroxy other than the above used as needed Compound and the melt phase polycondensation of carbonic diester reaction.
The melt phase polycondensation is known per se method, and details is recorded in such as Japanese Unexamined Patent Publication 2008-24919 Publication, Japanese Unexamined Patent Publication 2009-161746 publications, Japanese Unexamined Patent Publication 2009-161745 publications, International Publication No. 2011/06505 Number, in Japanese Unexamined Patent Publication 2011-111614 publications etc..The Copolycarbonate of the present invention can be according to described in these documents Method manufacture.
[2] resin combination
< thermoplastic resins >
In the present invention, the thermoplastic resin of specified rate is coordinated further preferably in above-mentioned polycarbonate resin.
The use level of polycarbonate resin and thermoplastic resin is the mass parts of 1 mass parts of polycarbonate resin~99 and heat The scope of the mass parts of 99 mass parts of plastic resin~1 is preferably the mass parts of 10 mass parts of polycarbonate resin~99 and thermoplasticity The mass parts of the mass parts of 90 mass parts of resin~1, more preferably 30 mass parts of polycarbonate resin~99 and 70 matter of thermoplastic resin Measure the mass parts of part~1, further preferably the mass parts of 50 mass parts of polycarbonate resin~99 and 50 mass parts of thermoplastic resin ~1 mass parts.If the use level of thermoplastic resin is excessive, plant origin degree may be decreased, if on the contrary, thermoplastic resin Use level it is very few, then may may not proceed sufficiently the improvement of polycarbonate resin.
Here, as thermoplastic resin, it can be cited for example that:Polyethylene terephthalate, poly terephthalic acid third The aromatic polyester-based resins such as diol ester, polybutylene terephthalate (PBT), polycyclohexylene's diformazan alcohol ester;Poly- breast The saturated polyesters such as the aliphatic polyester-based resins such as acid, poly butylene succinate, polycyclic hexane dimethanol-- cyclohexane dicarboxylic ester Resinoid;The aromatic polycarbonate resins formed by the various bisphenols such as bisphenol-A, bisphenol Z;By 3 (4), 8 (9)-bis- (hydroxyls Methyl) tricyclic [5.2.1.02,6] the ester ring type polycarbonate resin that is formed of the ester ring types dihydric alcohol such as decane;By 3,9- it is double (1, 1- dimethyl -2- hydroxyethyls) aliphatic poly that is formed of the heterocycles dihydric alcohol such as -2,4,8,10- four oxaspiro [5,5] hendecane The polycarbonate resins such as carbonates resin;6th, the fatty polyamides resinoid such as 66,46,12;The semiaromatics such as 6T, 6I, 9T The polyamide-based resins such as polyamide resinoid;Polystyrene resin, high impact polystyrene resinoid, acrylonitrile/benzene second Vinyl resin (AS), acrylonitrile/butadiene/styrene resinoid (ABS), acrylonitrile/ethylene, propylene (diene)/styrene resin (AES), the styrene resins such as crystallinity syndiotactic polystyrene resin;The acrylic resins such as PMMA and MBS;Low-density, in Density and high density polyethylene (HDPE), ethylene/methacrylic acid ester copolymer (EMA), ethylene/vinyl acetate (EVA), second The polyethylene copolymers resinoids such as alkene/glycidyl methacrylate copolymer (E/GMA);Polypropylene-based resin, 4- methylpents The olefine kind resins such as -1 resin of alkene, cyclic olefin polymer (COP) and cyclic olefine copolymer (COC);Polyacetal resin, polyamide acyl Imide resin, polyethersulfone resin, polyimide resin, polyphenylene oxide resin, polyphenylene sulfide, polyphenylene sulfone resins, polyether-ether-ketone The thermoplastic resins such as resin, liquid crystalline polyester resin, thermoplastic polyurethane resin, Corvic, fluororesin or they Mixture.
Among these, the polyester resin that is preferably made of aromatic polyester-based resin, saturated polyester resin etc. and It is made of aromatic polycarbonate resins etc. and without the structural unit from the dihydroxy compounds shown in above-mentioned formula (1) Polycarbonate resin.In addition, among these, as polyester resin, more preferable polyethylene terephthalate gathers to benzene The aromatic polyesters classes such as naphthalate, polybutylene terephthalate (PBT), polycyclohexylene's diformazan alcohol ester Resin is formed and as by aromatic polycarbonate resins etc. without from the dihydroxy compounds shown in above-mentioned formula (1) Structural unit polycarbonate resin, the aromatic copolycarbonate being more preferably made of the various bisphenols such as bisphenol-A, bisphenol Z Resinoid.
These thermoplastic resins can use a kind of or two or more uses of mixing, can be based on according to purpose of usage required The characteristics such as heat resistance, resistance to chemical reagents, the mouldability wanted suitably select to use.In addition it is also possible to use the unsaturationizations such as maleic anhydride It closes object and carries out graft modification or end modified rear use.
The > such as < additives
In the present invention, above-mentioned Copolycarbonate can coordinate heat stabilizer, antioxidant, ultraviolet light to inhale as needed Various additives, bladder regulator and other resins such as agent, light stabilizer, blueing agent etc. are received resin combination is made, and With together with the foaming agent of suitable foam forming method for foaming.
Specifically, in the present invention, molecular weight and molecular weight, form and aspect deterioration are generated when being molded in order to prevent etc., it can be in poly- carbon Acid esters coordinates heat stabilizer when being copolymerized.
As heat stabilizer, can enumerate such as phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acids and their ester.Specifically may be used To enumerate for example:Triphenyl phosphite, phosphorous acid three (nonyl phenyl) ester, phosphorous acid three (2,4- di-tert-butyl-phenyls) ester, Asia Tridecyl phosphate, three monooctyl ester of phosphorous acid, phosphorous acid three (octadecyl) ester, phosphorous acid didecyl list phenylester, phosphorous acid two are pungent Base mono-phemyol ester, phosphorous acid diisopropyl list phenylester, phosphorous acid monobutyl diphenyl, phosphorous acid list decyl diphenyl, Phosphorous acid list octyl diphenyl, double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphites, 2,2- methylene Double (4,6- di-tert-butyl-phenyls) octyl group phosphite esters, double (nonyl phenyl) pentaerythritol diphosphites, double (bis- tertiary fourths of 2,4- Base phenyl) pentaerythritol diphosphites, distearyl pentaerythrityl diphosphite, tributyl phosphate, triethyl phosphate, phosphorus Sour trimethyl, triphenyl phosphate, diphenyl phosphate list neighbour biphenyl ester, dibutylphosphoric acid ester, dioctylphosphoric acid ester, phosphoric acid diisopropyl Ester, 4,4 '-biphenylene diphosphinic acid four (2,4- di-tert-butyl-phenyls) ester, phosphniline dimethyl phthalate, phosphniline diethyl phthalate, phosphniline Sour dipropyl etc..
Wherein, preferably phosphorous acid three (nonyl phenyl) ester, trimethyl phosphate, phosphorous acid three (2,4- di-tert-butyl-phenyl) Ester, double (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites, double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythrites Diphosphites and phosphniline dimethyl phthalate.
These heat stabilizers can be used alone one kind, can also be used in combination of two or more.
In addition to the additive amount that heat stabilizer can add when except melt polymerization, further coordinated by additional.That is, If further coordinate phosphitylation after makrolon in the phosphorons acid compound with suitable equivalent, phosphate cpd to obtain Object is closed, then can avoid mist degree rising, coloring and the reduction of heat resistance during polymerization, can further coordinate substantial amounts of thermostabilization Agent is deteriorated so as to fulfill form and aspect are prevented.
Compared with 100 mass parts of Copolycarbonate, the use level of above-mentioned heat stabilizer is preferably 0.0001 mass parts Above, be more preferably more than 0.0005 mass parts, further preferably more than 0.001 mass parts, and preferably 1 mass parts with Under, it is more preferably 0.5 below mass part, further preferably 0.2 below mass part.
In addition, in the present invention, aoxidizing in order to prevent, antioxidant can be coordinated in Copolycarbonate.
As antioxidant, it can be mentioned, for example:Pentaerythrite four (3-thiopropionate), (the 3- lauryl sulphur of pentaerythrite four For propionic ester), glycerine -3- stearyl-thios propionic ester, the double [3- (3- tertiary butyl -5- methyl -4- hydroxy phenyls) of triethylene glycol Propionic ester], 1,6-HD double [3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester], [3- (3,5- bis- of pentaerythrite four Tert-butyl-hydroxy phenyl) propionic ester], octadecyl -3- (3,5- di-tert-butyl-hydroxy phenyls) propionic ester, 1,3,5- tri- Methyl -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene, N, N- hexamethylene bis (3,5- di-t-butyl -4- hydroxyl hydrogens Change cinnamamide), 3,5- di-tert-butyl-4-hydroxyl benzyls phosphonate ester-diethyl ester, three (3,5- di-t-butyl -4- hydroxyl benzyls Base) isocyanuric acid ester, 4,4 '-biphenylene diphosphinic acid four (2,4- di-tert-butyl-phenyls) ester, 3,9- it is double 1,1- dimethyl- 2- [β-(3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls) propionyloxy] ethyl } four oxaspiros (5,5) of -2,4,8,10-, 11 carbon Alkane etc..
These antioxidant can be used alone one kind, can also be used in combination of two or more.
Compared with 100 mass parts of Copolycarbonate, the use level of above-mentioned antioxidant be preferably 0.0001 mass parts with More than upper, more preferably 0.01 mass parts, and preferably 0.5 is below mass part, more preferably 0.3 below mass part.
In addition, in the present invention, in order to further improve in foam shaping by extrusion carried out from chill roll roller disengaging or Release property that person departs from when injection foaming is molded from mold etc. can coordinate releasing agent in Copolycarbonate.
As releasing agent, it can be cited for example that:The high-grade aliphatic ester of monohydric alcohol or polyalcohol, higher fatty acids, paraffin, Beeswax, olefines wax, the olefines wax containing carboxyl and/or carboxylic acid anhydride group, silicone oil, organopolysiloxane etc..
As high-grade aliphatic ester, preferably such as the monohydric alcohol of carbon number 1~20 or polyalcohol and carbon number 10~ The part ester or full ester that 30 saturated fatty acid is formed.
The part ester or full ester formed as monohydric alcohol or polyalcohol with saturated fatty acid, it can be cited for example that:Stearic acid Monoglyceride, two glyceride of stearic acid, glycerol stearate, stearic acid list sorbitol ester, stearyl stearate, behenic acids Monoglyceride, behenic acid Shan Yu ester, pentaerythritol monostearate, pentaerythritol tetrastearate, four pelargonate of pentaerythrite, Propylene glycol monostearate, stearyl stearate, palmitic acid palm ester, butyl stearate, methyl laurate, palmitic acid isopropyl Ester, Biphenthrin (biphenyl biphenate), sorbitan monostearate, stearic acid 2- ethylhexyls etc..
Wherein, preferably glyceryl monostearate, glycerol stearate, pentaerythritol tetrastearate, behenic acid Shan Yu Ester.
As higher fatty acids, the preferably such as saturated fatty acid of carbon number 10~30.As the aliphatic acid, Ke Yiju Go out myristic acid, lauric acid, palmitic acid, stearic acid, behenic acids etc..
These releasing agents can be used alone one kind, can also be used in combination of two or more.
Compared with 100 mass parts of makrolon, the use level of releasing agent is preferably more than 0.01 mass parts, more preferably It is more than 0.1 mass parts, and it is preferably 5 below mass part, more preferably 1 below mass part.
In addition, in the present invention, in order to prevent by UV-induced discoloration, Copolycarbonate can coordinate ultraviolet Light absorbers, light stabilizer.
As ultra-violet absorber, light stabilizer, it can be cited for example that:2- (2 '-hydroxyl -5 '-t-octyl phenyl) benzo Triazole, 2- (3- tertiary butyl -5- methyl -2- hydroxy phenyls) -5- chlorobenzotriazoles, 2- (5- methyl -2- hydroxy phenyls) benzo three Azoles, 2- [double (bis (alpha, alpha-dimethylbenzyl) base) phenyl of 2- hydroxyls -3,5-] -2H- benzotriazole, 2,2 '-di-2-ethylhexylphosphine oxide (4- isopropylbenzenes Base -6- benzotriazole phenyl), 2,2 '-TOPOT 2,2′ p phenylenebis (1,3- benzosAzoles -4- ketone) etc..
Above-mentioned ultra-violet absorber, light stabilizer can be used alone one kind, can also be used in combination of two or more.
Compared with 100 mass parts of Copolycarbonate, ultra-violet absorber, the use level of light stabilizer are preferably More than 0.001 mass parts, more than more preferably 0.01 mass parts, and preferably 2 below mass part, more preferably 0.5 mass Below part.
In addition, in the present invention, it, can be poly- in order to eliminate the yellow sense as caused by polymer, ultra-violet absorber etc. Coordinate blueing agent in carbonate resin.
As blueing agent, as long as the existing blueing agent that can be used in polycarbonate resin, have no it is specifically limited, But it is preferred that anthraquinone dyes.
Specifically, it can be cited for example that:13 [CA.No. (color index No) of solvent violet (Solvent Violet) 60725], solvent purple 31 (CA.No.68210), solvent violet 33 (CA.No.60725), solvent blue (Solvent Blue) 94 (CA.No.61500), solvent violet 36 (CA.No.68210), (" the Macrolex Violet of Bayer companies manufacture of solvent blue 97 RR "), solvent blue 45 (CA.No.61110) etc..
Above-mentioned blueing agent can be used alone one kind, can also be used in combination of two or more.
Compared with 100 mass parts of Copolycarbonate, the use level of blueing agent is usually 0.1 × 10-5More than mass parts, Preferably 0.1 × 10-4It is more than mass parts, and usually 2 × 10-1It is below mass part, more preferably 0.5 × 10-1Mass parts with Under.
In addition, in the present invention, in order to which Copolycarbonate is made smoothly to foam, bladder regulator can be coordinated.
As bladder regulator, it can be cited for example that:Talcum, silica, aluminium oxide, mica, calcium carbonate, wollastonite, The plate of montmorillonite, kaolin etc., powdered or fibrous inorganic compound.Above-mentioned inorganic compound can use such as silane Coupling agent, titante coupling agent, the silicon class compound with Si -- H bond, organosilicone compounds etc. are surface-treated. Than that described above, further preferably mixture of the acid salt of polybasic carboxylic acid, polybasic carboxylic acid and sodium carbonate or sodium acid carbonate etc. is used as gas Steep regulator.
Above-mentioned bladder regulator can be used alone one kind, can also be used in combination of two or more.
Compared with 100 mass parts of Copolycarbonate, the use level of bladder regulator is preferably more than 0.1 mass parts, It is more than more preferably 0.3 mass parts, and it is preferably 50 below mass part, more preferably 10 below mass part.
The cooperation of Copolycarbonate and various additives and other resins etc. in the present invention can pass through itself Known commonly used approach carries out.It can be cited for example that:Using rotary drum mixer, V-type blender, super mixer, The method or be dissolved in by above-mentioned each ingredient that nauta mixer, banbury mixers, mixing roller, extruder etc. are mixed Such as in the common good solvent such as dichloromethane in the state of the solution blending process that is mixed etc..
The Henry's constant > of < resin combinations
Resin combination is preferably carried out foaming and obtained by the formed body of the present invention, and the resin combination is 200 Carbon dioxide at DEG C is 2.5 × 10 compared with the Henry's constant of resin combination-3~4.0 × 10-3G (carbon dioxide)/g (trees Oil/fat composition) MPa.
According to Henry rules, at a certain temperature, solubility of the carbon dioxide (gas) in above-mentioned resin combination with Pressure under the environment is proportional.The rule can be represented by following formula.
C=kP (C:The solubility of gas, P:Pressure)
Here, the proportionality constant k in above-mentioned formula is Henry's constant.It can be said that if the value of Henry's constant were smaller, two Solubility of the carbonoxide in above-mentioned resin combination is also smaller, if the value is larger, carbon dioxide is in above-mentioned resin combination Solubility in object is also larger.
It should be noted that shown in the implementation item of the assay method of Henry's constant specifically as be described hereinafter.
Carbon dioxide of the above-mentioned resin combination used in the present invention at 200 DEG C is compared with above-mentioned resin combination Henry's constant [g (carbon dioxide)/g (resin combination) MPa] is preferably generally 2.5 × 10-3Above, be more preferably 2.6 × 10-3Above, it is most preferably 2.7 × 10-3More than, and preferably generally 4.0 × 10-3Below, 3.9 × 10 are more preferably-3With Under, further preferably 3.8 × 10-3Below, 3.7 × 10 are particularly preferably-3Below, it is most preferably 3.6 × 10-3Below.
By that there will be the above-mentioned resin combination of the Henry's constant of above range for foaming, can be foamed Multiplying power is high, impact resistance is good, that is, quality is particularly lightweight and the formed body of excellent strength.
If front describes, the resin combination with the Henry's constant of above range can be as desired by appropriate control Species and containing ratio of the copolymer composition of isobide processed etc. obtain.
[3] purposes of foam forming method, formed body etc.
In the present invention, above-mentioned resin combination can be sent out together with the foaming agent for being suitable for foam forming method Type is soaked to obtain the formed body of the present invention.
In the present invention, as foaming agent, it is not particularly limited, volatile foaming agent, the hair of inorganic can be used The arbitrary foaming agent such as infusion, decomposition-type foaming agent.
As volatile foaming agent, it can be cited for example that:Normal butane, iso-butane, pentane, isopentane, hexane etc. are low Grade aliphatic hydrocarbon compound;The ester ring type hydrocarbons compound such as cyclobutane, pentamethylene;The aromatic hydrocarbons chemical combination such as benzene,toluene,xylene Object;The lower aliphatics unitary alcoholic compound such as methanol, ethyl alcohol;The lower aliphatics ketone compound such as acetone, methyl ethyl ketone;Chloromethanes, Low boiling points halogenated hydrocarbon compounds such as the chloro- 1,1- Difluoroethanes of chloroethanes, 1- etc..
As the foaming agent of inorganic, it can be cited for example that:In gas shape, supercriticality, subcritical state Nitrogen, carbon dioxide, water of free position etc..
As decomposition-type foaming agent, as long as the hair of the gases such as nitrogen, carbon dioxide can be generated by pyrolysis Infusion is not particularly limited, it can be cited for example that:The azo-compounds such as Barium azodicarboxylate, azodicarbonamide, N, The carbonic acid such as hydrazine compounds, the sodium acid carbonates such as the nitroso compounds such as N '-dinitrosopentamethylene tetramine, 1,2- hydrazine diformamides Hydrogen salt etc..
Among these, the preferably nitrogen of supercriticality or subcritical state, carbon dioxide or their mixture.
Above-mentioned foaming agent can be used alone one kind, can also be used in combination of two or more.
The amount of foaming agent can suitably be determined according to the species and expansion ratio of foaming agent, compared with Copolycarbonate 100 mass parts are preferably more than 0.1 mass parts, more preferably more than 0.5 mass parts, and preferably 20 below mass part, more Preferably 10 is below mass part.
In the present invention, foam forming method is not particularly limited.
Although there are various foam forming methods, in general, foaming includes following each process.
1) process of (or being mixed into) foaming agent is dissolved in the polymer
2) process for generating bubble
3) make the process (process 3) of bubble growth mostly with process 2) be carried out at the same time)
4) process for immobilizing bubble
In general, foam forming method is roughly divided into two kinds.A kind of is intermittent foam forming method, as its an example, Can enumerate makes foaming agent contain the method for being immersed in and it being made to foam in formed body afterwards.The usual work of intermittent foam forming method Skill temperature is relatively low.In addition, the long time is needed in above-mentioned each process.
As foaming agent is contained be immersed in formed body after the method that foams, such as can by resin combination into Type body is placed in autoclave and adds in supercritical fluid, and the supercritical fluid is made then to reduce pressure containing being dipped into formed body, by This obtains foaming body.In addition, for the foaming agent to be foamed by heating, can be dipped into foaming agent is contained After in type body, foaming body is obtained by heating.
Another method is the foam forming method of continous way, can enumerate used extrusion shaping machine, injection moulding machine, The foam forming method of blow molding machine etc..The usual technological temperature of foam forming method of the continous way is higher.It is in addition, above-mentioned each The process required time is shorter.
As foam shaping by extrusion, it can be cited for example that:(a) resin combination is melted in an extruder with foaming agent Melt mixing, squeeze out molten resin from the circular die of extruder front end, formed using cylindric cooler (mold core) cylindric Foaming body, then the method cut along direction is squeezed out and sheet is made;(b) resin combination is carried out in an extruder with foaming agent Melting mixing squeezes out slabbing from the T-shaped mould head of extruder front end, then obtains picking up method of piece etc. with chill roll.
It should be noted that foaming agent uses after being mixed in advance with Copolycarbonate, it can also be in extruder Midway is pressed into.
As injection-expansion molded, it can be cited for example that:(c) foaming agent is mixed or is dissolved in molten in injection moulding machine In the resin combination for melting state, carry out making resin expanded while being filled into the side in mold during injection molding in mold Method;(d) foaming agent is mixed or is dissolved in the resin combination of molten condition in injection moulding machine, in injection fillers to mould When in tool, pressure of resin during by counter-pressure or injection etc. applies pressure to inhibit to foam, and then, utilizes drawer at movable side of mould Retrogressing, counter-pressure releasing or cooling when resin combination contraction etc. carry out pressure reduction and make its method to foam etc..
In the present invention, it is believed that in the makrolon with the structural unit from isobide, have and come from The Copolycarbonate of the structural unit of other dihydroxy compounds, the particularly glass transition temperature with particular range (Tg) Copolycarbonate, which has, is adapted to both above-mentioned intermittent foam forming method, continous way foam forming method Characteristic, i.e. there is appropriate gaseous solubility and gas diffusibility.Therefore, in the case where carrying out foaming, can obtain With sufficient expansion ratio and preferable foaming form (size, number density, the independence=do not connect bubble or connect and steep very of bubble Expanded moldings less), therefore it could be speculated that light weight, mechanical properties (elongation) good expanded moldings can be produced.
As described above, in the present invention, foam forming method can be intermittent foaming, can also be continous way hair Steep forming method, but more preferably continous way foam forming method.This is because, there is the knot from isobide in the present invention In the makrolon of structure unit, there is the Copolycarbonate of the structural unit from other dihydroxy compounds, be particularly Gaseous solubility and gas diffusion shown by the Copolycarbonate of glass transition temperature (Tg) with particular range Property is more suitable for continous way foaming forming technique.
In each process of foaming, in the process 1) foaming agent to be dissolved to (or being mixed into) to polymer in, gas Diffusivity is higher, and gas dissolves faster.I.e., it is possible to shorten the process required time.
In addition, in 3) process of bubble growth is made, the diffusivity of gas is higher, and the growth of bubble is faster.
If gas diffusibility is excessively high, the easy coarsening of bubble, when applying deformation to expanded moldings by external force, slightly Air pocket becomes breaking point, may decline mechanical properties (elongation).
If gas diffusibility is too low, bubble will not fully grow up, and expansion ratio will not improve, accordingly, it is possible to make light Quantification effect becomes smaller.
In the makrolon with the structural unit from isobide of the present invention, have from other dihydroxies Copolycarbonate, the poly- carbonic acid of the glass transition temperature (Tg) particularly with particular range for closing the structural unit of object Ester copolymer, although with the makrolon without the structural unit from other dihydroxy compounds and with from it The structural unit of its dihydroxy compounds but the Copolycarbonate phase with 145 DEG C or more of glass transition temperature (Tg) Than, since gaseous solubility is high, in gas dissolution process, more gases can be dissolved in the polymer.Therefore, It can expect the expanded moldings of acquisition more light weight.
On the other hand, in the case of gaseous solubility height, gas diffusibility is similarly higher in most cases.Gas is molten In the case that Xie Xinggao and gas diffusibility are also high, it is believed that easily generate the gas from formed body surface in foaming midway Body is deviate from, it is possible to create the thus defect of caused resin, rough surface or the bubble generated due to gas diffusibility is excessively high Coarsening, therefore not preferred gaseous solubility and gas diffusibility are excessively high.
In the makrolon with the structural unit from isobide of the present invention, have from other dihydroxies Copolycarbonate, the poly- carbonic acid of the glass transition temperature (Tg) particularly with particular range for closing the structural unit of object Ester copolymer, although with the makrolon without the structural unit from other dihydroxy compounds and with from it The structural unit of its dihydroxy compounds but the Copolycarbonate phase with 145 DEG C or more of glass transition temperature (Tg) Than, since gas diffusibility is high, in time shorter bubble growth process bubble can be made fully to grow up, and by Will not be excessively high in gas diffusibility, the form that preferably foams can be shown, thus it is speculated that light weight, mechanical properties can be obtained (elongation) good expanded moldings.
On the other hand, gaseous solubility and gas diffusibility can change according to temperature, but having in the present invention In the makrolon of structural unit from isobide, there is the poly- carbonic acid of the structural unit from other dihydroxy compounds Ester copolymer, particularly with particular range glass transition temperature (Tg) Copolycarbonate, with without from Although the makrolon of the structural unit of other dihydroxy compounds, with the structural unit from other dihydroxy compounds but Copolycarbonate and common bisphenols makrolon phase with 145 DEG C or more of glass transition temperatures (Tg) Than due to that can be molded at a lower temperature, gas diffusivity has suitable scope, so as to avoid because of gas Coarsening of bubble that diffusivity is excessively high and generates etc..
In the present invention, it is preferred to using above-mentioned foaming agent, by with the foam-injection that die cavity is expanded by above-mentioned tree Oil/fat composition carry out foaming, thus come obtain the present invention formed body.
In this case, as injection-expansion molded, it can be cited for example that:(a) foaming agent is mixed in injection moulding machine Or be dissolved in the resin combination of molten condition, it carries out making resin expanded while being filled into during injection molding in mold Method in mold;(b) foaming agent is mixed or is dissolved in the resin combination of molten condition in injection moulding machine, noted It penetrates when being filled into mold, pressure of resin during by counter-pressure or injection etc. applies pressure to inhibit to foam, and then, utilizes Retrogressing (moving back core (U ア バ ッ Network)) resin when the expansion of die cavity, the releasing of counter-pressure or cooling of generations of drawer at movable side of mould Contraction of composition etc. carries out pressure reduction and makes its method to foam etc..
In this case, foaming agent is mixed or is dissolved in the resin combination of molten condition in injection moulding machine by above-mentioned (b) In object, when in injection fillers to mold, pressure of resin during by counter-pressure or injection etc. applies pressure to inhibit to foam, Then, pressure reduction is carried out using contraction of resin combination when the retrogressing of drawer at movable side of mould, the releasing of counter-pressure or cooling etc. And make in the method that it foams, foaming agent is mixed or is dissolved in preferably in injection moulding machine the resin combination of molten condition In, when in injection fillers to mold, pressure of resin during by counter-pressure or injection etc. applies pressure to inhibit to foam, so By using retrogressing (moving back core) of drawer at movable side of mould etc. die cavity expansion is made to make the method that it foams afterwards.
Cavity volume after die cavity expansion is usually more than 1.1 compared with the cavity volume that resin combination is filled when completing Times, be preferably more than 1.5 times, more preferably 2.0 times or more, most preferably 2.5 times or more, and usually less than 100 times, it is excellent It elects less than 50 times, more preferably less than 30 times as, be most preferably less than 20 times.
If the amount of expansion of die cavity is few, light weight effect may be made to become smaller, if the amount of expansion of die cavity is more, production of foaming The swell increment of raw resin combination is less than the amount of expansion of die cavity, so as to obtain the expanded moldings of desired size.
The time that die cavity starts expansion is not particularly limited, and fills completion into mold usually with resin and (fills out simultaneously substantially Charge within front and rear 0.1 second) or for filling after the completion of, after the completion of the filling in the case of, for after the completion of filling 10.0 It is preferably within 5.0 seconds, more preferably within 3.0 seconds within second.If the time that die cavity starts expansion has relatively filled Into significantly shifting to an earlier date, then cause foaming by the expansion of die cavity since the state of underfill in mold, accordingly, it is possible to can not obtain Expanded moldings with desired size and even density, if the time relatively filling that die cavity starts expansion is completed significantly Fall behind, then generated before die cavity is expanded because the viscosity that the cooling zone of resin is come rises, foaming may be made to become difficult.
In the case where the amount of expansion of die cavity is equal with the swell increment of resin caused by foaming, due to can obtain have with Die cavity expansion after mold volumes with isometric(al) expanded moldings, therefore for example in a thickness direction implement die cavity expansion In the case of, can use " thickness of expanded moldings " with " die cavity expansion before mold thickness " the ratio between [(expanded moldings Thickness)/(thickness of the mold before die cavity expansion)] and " expansion ratio " is defined, it should " expansion ratio " and (resin before foaming The density of composition)/(density of expanded moldings) equivalent.
It as long as the temperature resin combination of foaming is capable of the temperature of foaming, is not particularly limited, leads to Often it is 80 DEG C or more, more preferably 100 DEG C or more, and usually less than 300 DEG C, more preferably less than 260 DEG C.
In more detail, the lower limit of the temperature of foaming is preferably than the glass transition temperature (Tg) of Copolycarbonate More than high 5 DEG C of temperature, more than more preferably high 10 DEG C of temperature, in addition, the upper limit of the temperature of foaming is preferably than the copolymerization Below the temperature of 200 DEG C of the Tg high of object, below more preferably high 150 DEG C of temperature.
Temperature during by making foaming is above range, shaping can be had while the thermal decomposition of resin is inhibited It is expected the foaming body of expansion ratio.If temperature is excessively high, resin may thermally decompose, if temperature is too low, resin glues Degree is high, therefore in the presence of the tendency that foaming becomes difficult.
In addition, in the formed body of the present invention, expansion ratio, bubble footpath (セ Le footpath) etc. are not particularly limited, Ke Yitong Cross the additive amount for for example adjusting foaming agent, forming method is suitably set.Specifically, expansion ratio be usually 1.1 times or more, Preferably 1.5 times or more, more preferably 2.0 times or more, and usually less than 100 times, be preferably less than 50 times, be more preferably Less than 30 times.
It should be noted that the expansion ratio in the present invention is the value acquired according to the method implemented shown in item.Separately Outside, the shape of foaming body (formed body) according to purposes etc. it is not also specifically limited, can suitably determine.
In the formed body of the present invention, multiple stratification or coextrusion can also be carried out each other to nonfoamed layer, foaming layer, to table The resins such as the unexpanded makrolon in face, polyethylene terephthalate are laminated.In addition, in the situation of injection-molded article Under, the non-foamed piece of makrolon etc. can also be inserted into the one or both sides in mold, then carry out injection-expansion molded, system Into foaming body and the integrated molding product of non-foamed piece.At this point it is possible to printing, hard painting, imparting are carried out using in non-foamed on piece The molded product of weatherability etc..In addition, the processing such as these formed body surfaces can also be printed, antistatic process, hard painting.
The formed body of the present invention particularly expansion ratio is high, impact resistance is good, i.e. is particularly light weight and intensity is excellent It is different, therefore, it can be used for component, containers for food use, light reflecting material, the heat-insulated material in each field such as electric and electronic, automobile, building Material, acoustic material, padded coaming, low specific gravity material, fuel cell separator plate, low-dielectric, low specific gravity material, seperation film etc..
[present invention plays the reasons why effect]
In the present invention, it is believed that in the makrolon with the structural unit from isobide, have from other The Copolycarbonate of the structural unit of dihydroxy compounds, the particularly glass transition temperature (Tg) with particular range Copolycarbonate have suitable gaseous solubility and gas diffusibility.Therefore, in the case where carrying out foaming, It can obtain with sufficient expansion ratio and the preferable foaming form (size of bubble, number density, independence=do not connect bubble Or even steep seldom) expanded moldings, therefore it could be speculated that mechanical properties (elongation) good foaming can be produced Body.
Embodiment
Hereinafter, the present invention is described in more detail by embodiment, but as long as without departing from the purport of the present invention, the present invention is not It is limited to following embodiment.It should be noted that the value of the various manufacturing conditions and evaluation result in following embodiments refers to this The preferred value of the upper limit or lower limit in invention embodiment, preferred scope can be the above-mentioned upper limit or lower limit value with it is following Value in the value or embodiment of embodiment is combined with each other and defined scope.
< glass transition temperatures (Tg) >
Using differential scanning calorimeter (METTLER companies manufacture DSC822), will about 10mg samples with 10 DEG C/min's Heating rate heats to measure, and based on JIS K 7121 (1987) standard, extrapolation glass transition start temperature has been obtained, described Extrapolation glass transition start temperature is by straight line obtained from the base line extension to high temperature side of low temperature side and in glass transition The gradient of curve in stepped changing unit reaches the temperature of the intersection point for the tangent line drawn at maximum point.
< color b values >
Using colour photometer (300A that Japanese electricity Se Co., Ltd. manufactures), die colors are determined.
The chip of specified rate is put into glass sample pond, is measured by reflection measurement, determines b values.
The numerical value is smaller, and yellow degree is smaller.
< reduced viscositys >
The DT-504 types automatic viscometer (Ubbelodhe type viscosimeter) manufactured using central physics and chemistry Co., Ltd., and use The mass ratio of phenol and 1,1,2,2- tetrachloroethanes is 1:1 mixed solvent as solvent, at 30.0 DEG C ± 0.1 DEG C of temperature into Measure is gone.Concentration precision is adjusted to 1.00g/dl.
Sample dissolves 30 minutes while stirring at 120 DEG C, is used to measure after cooling.
Time t is passed through by solvent0, solution relative viscosity η rel are obtained by time t according to the following formula,
η rel=t/t0(g·cm-1·sec-1)
Inherent viscosity η sp have been obtained by relative viscosity η rel according to the following formula again.
η sp=(η-η0)/η0=η rel-1
With inherent viscosity η sp divided by concentration c (g/dl), reduced viscosity (reduced viscosity) η red have been obtained according to the following formula.
η red=η sp/c
The numerical value is higher, and molecular weight is bigger.
5% hot loss of weight temperature > of <
The TG-DTA (SSC-5200, TG/DTA220) manufactured using Seiko Electronics Co., Ltd, aluminium is placed on by 10mg samples In container, (200ml/ points of nitrogen flow) is warming up to 450 DEG C with 10 DEG C/minute of heating rate to carry out from 30 DEG C under nitrogen atmosphere It measures, temperature when reducing by 5% mass has been obtained.
The temperature is higher, is more not easy to thermally decompose.
< Izod impact strengths >
Using Custom Scientific companies manufacture Minimax injection moulding machine CS-183MMX, temperature 240~ The long 31.5mm of injection molding, width 6.2mm, the test film of thickness 3.2mm at 300 DEG C cut out the notch of deep 1.2mm with slotting machine, make For test film.
For the test film, the Minimax lzod impact testers manufactured using Custom Scientific companies CS-183TI types determine the nicked Izod impact strength at 23 DEG C.
The numerical value is bigger, and impact strength is bigger, is more not easily broken.
The gas generated > of <
Using wide 8cm, long 8cm, thickness 0.5mm spacing board, using hot press 200~250 DEG C of hot pressing temperature, preheating 1 ~3 minutes, under conditions of pressure 20MPa for be dried in vacuo at 100 DEG C 5 it is small when resin sample 8g pressurize 1 minute, so It is taken out afterwards together with spacing board, cooling 3 minutes of being pressurizeed using water pipe cooling formula press under pressure 20MPa has made sheet material. The sample of wide 1cm, long 2cm are cut out by the sheet material.Its thickness is 1mm.
Using heat desorption-GC/MS Analysis method (TDS-GC/MS) to the Specimen Determination generation gas.Make For measurement device, the TDS2 manufactured using GERSTEL companies, at 250 DEG C of desorption temperature of heating, 10 minutes, -130 DEG C of trap temperature Implement measure.
Sample is put into glass container (chamber), in 30 minutes, helium 60mL/ points of condition with catching at 110 DEG C Collector Tenax-TA has trapped generated gas.
It, as chromatographic column, is used as GC/MS, the HP6890/5973N that Agilent companies is used to manufacture HP-VOC:0.32 × 60m, 1.8 μm of df, keep after five minutes at 40 DEG C, 280 DEG C are warming up to 8 DEG C/minute, then at 280 DEG C It is lower to be kept for 25 minutes, it is determined.Carrier gas divides for helium 1.3mL/.
Gas generated is the phenol that distills out and to come from per unit beyond the benzaldehyde of phenol when being manufactured to remove The total of area generates gauge, is obtained according to the scaled value based on toluene.
< pencil hardness >
Using surface measurements machine Tribogear, the model 14DR that Xin Dong science Co., Ltd. manufactures as measurement device, base It is determined under the following conditions in 5600 standards of JIS K.
Load 750g
Finding speed 30mm/min
Mensuration distance 7mm
Pencil uses the UNI that Mitsubishi Pencil K. K manufactures.
Pencil hardness uses 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B.
Measure has carried out 5 times, and most soft hardness is as measure substance in the pencil hardness for generating damage using 2 times or more Pencil hardness.
< apparent densities >
The balance XS204 manufactured using METTLER TOLEDO companies (uses gravity test component according to Archimedes method (kit), room temperature, aqueous solvent) determine the density before foaming and the density after foaming.It should be noted that it is following, this is apparent Density mark is " density ".
1 > of < expansion ratios
By " density before foaming " compared with the ratio between " density after foaming " [(density before foaming)/(close after foaming Degree)] it is used as " expansion ratio ".
2 > of < expansion ratios
By the ratio between " thickness of expanded moldings " and " thickness of the mold before die cavity expansion " [(thickness of expanded moldings Degree)/(thickness of the mold before die cavity expansion)] it is used as " expansion ratio ".
3 > of < expansion ratios
(situation based on the foaming for moving back the progress of core method)
By the ratio between " thickness of expanded moldings " and " thickness of the mold before die cavity expansion " [(thickness of expanded moldings Degree)/(thickness of the mold before die cavity expansion)] it is used as " expansion ratio ".
(situation based on the foaming that short injection carries out)
By the ratio between " thickness of expanded moldings " and " thickness for the mold that can be injected entirely " [(thickness of expanded moldings Degree)/(thickness for the mold that can be injected entirely)] it is used as " expansion ratio ".
The tension test > of resin before < foamings
Using above-mentioned injection moulding machine in temperature 240 DEG C~300 DEG C injection molding parallel portion length 9mm, parallel portion diameters The tension test sheet of 1.5mm is stretching speed using the cupping machine CS-183TE types that Custom Scientific companies manufacture Tension test is carried out under conditions of degree 1cm/ point, elongation, tensile yield strength when determining surrender, tensile yield springform Elongation when amount and fracture.
Above-mentioned each numerical value is bigger, with intensity, extensibility.
The tension test > of formed body after < foamings
It is long 63.5mm, width 16mm to be cut expanded moldings using sawing machine, and rectangular shape is made.At this point, original Expanded moldings width cut from middle body, in length direction from positioned at the portion of cast gate (gate) side half Divide and cut so that the length direction of expanded moldings originally becomes the length direction of the formed body after cutting.Then, make The coupons maker IDT-3 types manufactured with BALDWIN companies of Japan cut obtained rectangular formed body, obtain Arrived parallel minister 20mm, the wide 8mm of parallel portion, experiment length of a film 80mm dumb-bell shape test film.Use Toyo Co., Ltd.'s essence Mechanism makees manufactured cupping machine STROGRAPH VG10-E types, under conditions of 50mm/ points of tensile speed to acquired Test film carry out tension test, determine elongation during fracture.The numerical value is bigger, more with extensibility.
< Henry's constants >
After resin is made fully to dry, (pressed using forming machine for example, Co., Ltd.'s well member makes manufactured, desktop shaping Machine), pressurize under given temperature (such as 180 DEG C~280 DEG C), de- pressure come make do not have bladdery test film (such as 20mm φ, Thick 1mm~3mm), using magnetic suspension balance measurement device (Germany, the BEL P/O 152 of RUBOTHERM companies manufacture), in temperature Mass change when under 200 DEG C of degree, the carbon dioxide atmospheres of 5MPa~20MPa pressure limits in sample containing carbon dioxide into Row measures, it is possible thereby to which solubility of the carbon dioxide compared with resin is obtained.
Henry rules:In the relational expression of C=kP, the carbon dioxide that will be obtained according to the method described above by least square method It is fitted, is obtained with pressure P (MPa) compared with the gas solubility C (g (carbon dioxide)/g (resin combination)) of resin Henry's constant k.
It should be noted that in following Production Example 1~7, isobide is by Roquette used in reaction Freres companies manufacture or are manufactured by three photochemistry Co., Ltd., and 1,4-CHDM is manufactured by Eastman companies, carbon Diphenyl phthalate is manufactured by Mitsubishi chemical Co., Ltd, and Tricyclodecane Dimethanol is manufactured by Celanese companies, cesium carbonate, calcium acetate Monohydrate and 1,6-HD are manufactured by Wako Pure Chemical Industries, Ltd..
In addition, the abbreviation of the compound used in the record of following Production Example 1~7 is as follows.
ISB:Isobide
1,4-CHDM:1,4 cyclohexane dimethanol
TCDDM:Tricyclodecane Dimethanol
1,6-HD:1,6-HD
DPC:Diphenyl carbonate
< Production Examples 1:The manufacture > of Copolycarbonate (PC-1)
Method described in embodiment 1 based on Japanese Unexamined Patent Publication 2009-161746 publications is manufactured as follows.
27.7 mass parts of ISB (0.516 mole) are put into reaction vessel, (0.246 rubs 13.0 mass parts of 1,4-CHDM You), 59.2 mass parts of DPC (0.752 mole) and the cesium carbonate 2.21 × 10 as catalyst-4Mass parts (1.84 × 10-6 Mole), the process of following paragraph 1 as reaction has been carried out under nitrogen atmosphere:Heating tank temperature is heated to 150 DEG C, root According to needing to make dissolution of raw material (about 15 minutes) while stirring.
Then, pressure is made to become 13.3kPa (absolute pressure, similarly hereinafter) from normal pressure, with 1 it is small when rise to heating tank temperature 190 DEG C, while the phenol of generation is discharged to outside reaction vessel.
After reaction vessel is integrally kept for 15 minutes at 190 DEG C, the 2nd section following of processes has been carried out:Hold reaction Pressure in device is 6.67kPa, with 15 minutes heating tank temperature is made to rise to 230 DEG C, and the phenol of generation is discharged to reaction holds Outside device.Since the stirring torque of mixer rises, 250 DEG C were warming up to 8 minutes, then the phenol of generation is removed, therefore, reaction Pressure in container reaches below 0.200kPa.After the stirring torque for reaching given, reaction terminates, and the reactant of generation is squeezed Go out into water, obtained the particle of Copolycarbonate (PC-1).
Carbon dioxide at 200 DEG C is 3.4 compared with the Henry's constant of obtained Copolycarbonate (PC-1) ×10-3G (carbon dioxide)/g (resin combination) MPa, reduced viscosity 1.007dl/g, glass transition temperature 124 DEG C, color b values be 8.8.
In addition, being molded at 245 DEG C, 90 DEG C of mold temperature to the Copolycarbonate (PC-1), machine has been obtained Tool evaluation of physical property is with test film (2 kinds).The evaluation of mechanical properties has been carried out using these test films, it is as a result as follows:Tensile yield Intensity is 84MPa, tensile yield elasticity modulus is 748MPa, surrender when elongation be 16%, fracture when elongation be 30%, Chinese mugwort It is 227J/m to help moral impact strength2
In addition, the 5% hot loss of weight temperature of the Copolycarbonate (PC-1) under nitrogen atmosphere is 344 DEG C.Phenol component In addition it is gas generated be 3.7ng/cm2, the dihydroxy from addition to the dihydroxy compounds shown in formula (1) is not detected The generation gas of based compound.
< Production Examples 2:The manufacture > of Copolycarbonate (PC-2)
In Production Example 1, except being changed to 19.7 mass parts of ISB (0.363 mole), 21.6 mass parts of Isosorbide-5-Nitrae-CHDM (0.404 mole), 58.8 mass parts of DPC (0.741 mole), the cesium carbonate 2.19 × 10 as catalyst-4Mass parts (1.82 ×10-6Mole) beyond, implement in the same manner as Production Example 1.
Carbon dioxide at 200 DEG C is 3.7 compared with the Henry's constant of obtained Copolycarbonate (PC-2) ×10-3G (carbon dioxide)/g (resin combination) MPa, reduced viscosity 1.196dl/g, glass transition temperature 101 DEG C, color b values be 7.7.
In addition, being molded at 245 DEG C, 80 DEG C of mold temperature to the Copolycarbonate (PC-2), machine has been obtained Tool evaluation of physical property is with test film (2 kinds).The evaluation of mechanical properties has been carried out using these test films, it is as a result as follows:Tensile yield Intensity is 66MPa, tensile yield elasticity modulus is 595MPa, surrender when elongation be 16%, fracture when elongation be 27%, Chinese mugwort It is 293J/m to help moral impact strength2.The 5% hot loss of weight temperature of the Copolycarbonate (PC-2) under nitrogen atmosphere is 345 DEG C.
< Production Examples 3:The manufacture > of Copolycarbonate (PC-3)
Method described in embodiment 13 based on Japanese Unexamined Patent Publication 2009-161746 publications is manufactured as follows.
26.9 mass parts of ISB (0.483 mole) are put into reaction vessel, (0.211 rubs 15.8 mass parts of TCDDM You), 57.4 mass parts of DPC (0.704 mole) and the cesium carbonate 2.14 × 10 as catalyst-4Mass parts (1.73 × 10-6 Mole), the process of following paragraph 1 as reaction has been carried out under nitrogen atmosphere:Heating tank temperature is heated to 150 DEG C, root According to needing to make dissolution of raw material (about 15 minutes) while stirring.
Then, with 40 minutes by pressure from atmospheric depressurized to 13.3kPa, with 40 minutes heating tank temperature was made to rise to 190 DEG C, while the phenol of generation is discharged to outside reaction vessel.
After reaction vessel is integrally kept for 15 minutes at 190 DEG C, the 2nd section following of processes has been carried out:With 30 minutes Heating tank temperature is made to rise to 220 DEG C.Into heating after ten minutes, the pressure made with 30 minutes in reaction vessel is 0.200kPa Hereinafter, come out the phenol distillation of generation.After reaching given stirring torque, reaction was completed, and the reactant generated is squeezed out Into water, the particle of Copolycarbonate has been obtained.
The reduced viscosity of obtained Copolycarbonate (PC-3) is 0.640dl/g, glass transition temperature 126 DEG C, color b values be 4.6.
In addition, being molded at 245 DEG C, 90 DEG C of mold temperature to the Copolycarbonate (PC-3), machine has been obtained Tool evaluation of physical property is with test film (2 kinds).The evaluation of mechanical properties has been carried out using these test films, it is as a result as follows:Tensile yield Intensity is 89MPa, tensile yield elasticity modulus is 834MPa, surrender when elongation be 15%, fracture when elongation be 76%, Chinese mugwort It is 48J/m to help moral impact strength2
In addition, the 5% hot loss of weight temperature of the Copolycarbonate (PC-3) under nitrogen atmosphere is 348 DEG C.
It is in addition, gas generated for 4.5ng/cm beyond phenol component2, it is not detected from except general formula (1) Suo Shi Dihydroxy compounds beyond dihydroxy compounds generation gas.In addition, pencil hardness is F.
< Production Examples 4:The manufacture > of Copolycarbonate (PC-4)
In Production Example 3, except being changed to 18.7 mass parts of ISB (0.327 mole), 25.6 mass parts of TCDDM (0.333 mole), 55.8 mass parts of DPC (0.666 mole) and the cesium carbonate 2.08 × 10 as catalyst-4Mass parts (1.63×10-6Mole) beyond, implement in the same manner as Production Example 3.
The reduced viscosity of obtained Copolycarbonate (PC-4) is 0.785dl/g, glass transition temperature 110 DEG C, color b values be 4.7.
In addition, being molded at 245 DEG C, 90 DEG C of mold temperature to the Copolycarbonate (PC-4), machine has been obtained Tool evaluation of physical property is with test film (2 kinds).The evaluation of mechanical properties has been carried out using these test films, it is as a result as follows:Tensile yield Intensity is 79MPa, tensile yield elasticity modulus is 807MPa, surrender when elongation be 13%, fracture when elongation be 18%, Chinese mugwort It is 58J/m to help moral impact strength2
In addition, the 5% hot loss of weight temperature of the Copolycarbonate (PC-4) under nitrogen atmosphere is 349 DEG C.
< Production Examples 5:The manufacture > of Copolycarbonate (PC-5)
Method described in embodiment 1 based on Japanese Unexamined Patent Publication 2011-111614 publications is manufactured as follows.
Possess agitating paddle and be controlled in 100 DEG C reflux condenser polymerizing reactor in add in ISB and 1,6- HD, cause through distillation purifying chloride ion concentration be the DPC of below 10ppb and calcium acetate monohydrate so that with mole Than counting ISB/1,6-HD/DPC/ calcium acetates monohydrate=0.85/0.15/1.00/2.0 × 10-6, it has been sufficiently carried out nitrogen displacement (0.0005~0.001vol% of oxygen concentration).Then, heated with thermal medium, start to stir at the time of temperature reaches 140 DEG C inside It mixes.40 minutes after starting to warm up, interior temperature reaches 210 DEG C, and control is proceeded by the time of temperature reaches 210 DEG C inside, to keep being somebody's turn to do Temperature starts simultaneously at decompression, and when reaching 90 minutes after 210 DEG C, pressure reaches 13.3kPa, keeps the pressure and further keeps 30 minutes.The phenol vapor of by-product is imported into 100 DEG C of reflux condenser while polymerisation, will be in phenol vapor If the monomer component of the dry measure contained returns to polymer reactor, uncooled phenol vapor continues to imported into 45 DEG C of condenser In recycled.
The contents with nitrogen for having carried out oligomeric materialization as described above is recovered into pressure to atmospheric pressure, is then transferred to and possesses It agitating paddle and is controlled in 100 DEG C of another polymerizing reactor of reflux condenser, starts to warm up and depressurize, with 50 minutes It is 230 DEG C, pressure 200Pa to make interior temperature.Then, by 20 minutes pressure was made to reach given stirring power for below 133Pa At the time of with nitrogen recover pressure, content extract in the form of strand, with rotatably switching to particle has been made.
The reduced viscosity of obtained Copolycarbonate (PC-5) is 0.4299dl/g, glass transition temperature 122 DEG C, color b values be 12.22.
< Production Examples 6:The manufacture > of Copolycarbonate (PC-6)
In Production Example 5, except according to molar ratio computing ISB/1,6-HD/DPC/ calcium acetates monohydrate=0.70/ 0.30/1.00/2.0×10-6Mode fed beyond, implement in the same manner as Production Example 5.
The reduced viscosity of obtained Copolycarbonate (PC-6) is 0.4655dl/g, glass transition temperature 86 DEG C, color b values be 15.10.
< Production Examples 7:The manufacture > of makrolon (homopolymer) (PC-7)
Method described in embodiment 27 based on Japanese Unexamined Patent Publication 2009-161746 publications is manufactured as follows.
Using 40.1 mass parts of ISB (0.581 mole), 59.9 mass parts of DPC (0.592 mole), as the carbon of catalyst Sour caesium 2.23 × 10-4Mass parts (1.45 × 10-6Mole) put into reaction vessel, while stirring 150 are heated to from room temperature DEG C, it is dissolved (about 15 minutes).
Then, pressure is made to reach 13.3kPa from normal pressure, with 1 it is small when temperature is made to rise to 190 DEG C, while by the benzene of generation Phenol is discharged to outside system.After 190 DEG C are kept for 15 minutes, reactor pressure is made to make heating bath temperature with 15 minutes for 6.67kPa Degree rises to 230 DEG C, and the phenol of generation is discharged.Since stirring torque rises, 250 DEG C were warming up to 8 minutes, it further will production Raw phenol removes, and therefore, vacuum degree has reached below 0.200kPa.After the stirring torque for reaching given, reaction was completed, thinks Reactant is expressed into water and obtains particle, but due to that can not squeeze out, is taken out with bulk.
Carbon dioxide at 200 DEG C is 2.6 × 10 compared with the Henry's constant of obtained makrolon (PC-7)-3g (carbon dioxide)/g (resin combination) MPa, reduced viscosity 0.679dl/g, glass transition temperature are 160 DEG C, color b It is worth for 13.0, compared with the makrolon of Production Example 1~7, b values are high, are colored as brown.
Further, which at 265 DEG C is molded, has carried out mechanical properties evaluation test film (2 Kind) take.The evaluation of mechanical properties has been carried out using these test films, it is as a result as follows:Tensile yield strength is 105MPa, draws Stretch surrender elasticity modulus be 353MPa, surrender when elongation be 17%, fracture when elongation be 31%, Izod impact strength is 11J/m2, understood compared with Production Example 1~7, Izod impact strength is significant lower.
In addition, the 5% hot loss of weight temperature of the makrolon (PC-7) under nitrogen atmosphere is 339 DEG C.
< embodiments 1-1~1-6, comparative example 1-1 >
The resin that Production Example 1~7 obtains is dried in vacuo at 80 DEG C 12 it is small when, then carried out at 180 DEG C~230 DEG C Extrusion forming, has made the sheet material of thick 1mm.The sheet material of making is cut into 30mm square, as test film.Make test film at 80 DEG C It is lower vacuum drying 6 it is small when, determine density, then put into the pressure vessel of room temperature.It will be carried out in container with carbon dioxide After displacement, 10MPa is pressurized to, is made in test film containing being soaked with carbon dioxide.When 2 is small after 30 minutes, pressure vessel is opened Pressure release valve, be slowly decompressed to atmospheric pressure, test film then taken out from pressure vessel.The test film of taking-up is impregnated into and is added Heat makes its foaming in 1 minute into the oil bath of+20 DEG C or so of glass transition temperature (Tg), and being then impregnated into water stops foaming Only, expanded moldings have been taken out.After when drying 12 is small at 80 DEG C by the expanded moldings of taking-up, density is determined.
Table 1 be illustrated that the composition of each resin, glass transition temperature (Tg), oil bath temperature used in foaming, The difference of oil bath temperature and Tg, density (g/cm3), expansion ratio.
It should be noted that expansion ratio is measured based on expansion ratio 1.
Table 2 is illustrated that the character of the composition of polycarbonate resin, condition of molding and expanded moldings.Need what is illustrated Be, " the elongation during fracture of polycarbonate resin " to specifications described in fracture of the method to the resin before foaming When elongation be determined.
As shown in Table 1, embodiment 1-1~1-6 Copolycarbonate (have structural unit from isobide and The makrolon of structural unit from other dihydroxy compounds) on 15 DEG C higher than glass transition temperature (Tg)~24 DEG C of left sides At a temperature of the right side, there is foam performance excellent as 1.4 times~3.5 times.In addition, obtained in embodiment 1-1~1-6 into Type body (expanded moldings) has excellent mechanical property.
On the other hand, it is known that the PC-7 (homopolymer of isobide) of comparative example 1-1 is than glass transition temperature (Tg) Expansion ratio at high 20 DEG C of temperature (180 DEG C) is 1.07, compared with embodiment 1-1~1-6, foam performance substantially compared with Difference.
It is believed that the above results be due to, compared with the homopolymer of isobide, isobide and other dihydroxy chemical combination The gaseous solubility increase of the copolymer of object.
Comparative example 1-1 is equivalent to the embodiment 1,2 of patent document 3 (Japanese Unexamined Patent Publication 2009-964 publications).In patent In document 3, for " density " of embodiment 1,2 (foam molded product of isobide homopolymer), describe " in embodiment 1 For 650kg/m3", " be in example 2 590kg/m3", with the ratio that carbon dioxide has been used to be recorded as the application of foaming agent It is different compared with example 1, be use compared with carbon dioxide to the higher liquefied butane gas of the dissolubility of resin as foaming agent into The result ([0098] of patent document 3, [table 2] of [0100] section) of row foaming.In contrast, come in having for the present application From in the makrolon of the structural unit of isobide, for having the poly- carbon of the structural unit from other dihydroxy compounds For acid ester copolymer, the particularly makrolon of the glass transition temperature (Tg) with particular range, dissolubility is being utilized In the case that the carbon dioxide lower than butane is as foaming agent, it is known that density can be obtained as 0.374g/cm3~1.013g/cm3And Expanded moldings with high foamability.
Wherein, the glass transition temperature (Tg) of the makrolon used in embodiment 1 (A-1 ingredients) of patent document 3 The glass transition temperature (Tg) of makrolon (A-2 ingredients) to be used in 156 DEG C, embodiment 2 is 164 DEG C of (patent documents 3 [0090]~[0093] section).
As described above, from patent document 3, there is the vitrifying of the makrolon of the structural unit from isobide Transition temperature (Tg) is high, and carrying out foam shaping by extrusion needs high temperature as 250 DEG C.In contrast, in the present application, by Then in the makrolon with the structural unit from isobide with the structure from other dihydroxy compounds The Copolycarbonate of unit, particularly with particular range glass transition temperature (Tg) Copolycarbonate into Row foaming, it can thus be assumed that, compared with the homopolymer of isobide, foaming can be carried out at a lower temperature.
In addition, the glass transition temperature (Tg) of the makrolon (A-4 ingredients) of the Production Example 4 of patent document 3 is 138 DEG C ([0095] section of patent document 3).The A-4 ingredients show " being unable to even foaming " ([0099] of patent document 3 at 230 DEG C The comparative example 5 of section).It can thus be assumed that for the comparative example 5 of patent document 3, due to being glued when glass transition temperature is low Spend small, therefore the retentivity of bubble is poor, show can not even foaming (that is, foaminess is poor).
In contrast, found in the present application:It is right in makrolon with the structural unit from isobide In the Copolycarbonate with the structural unit from other dihydroxy compounds, the particularly glass with particular range For the Copolycarbonate for changing transition temperature (Tg), as described above with particularly good gaseous solubility and shock resistance Property, it can obtain light weight and the formed body of mechanical strength.These are the fact is that the fact that disclosed with patent document 3 is entirely different Accident the fact, the fact that the patent document 3 is open, is as follows:If different sorb is come to having in specific temperature range Melt viscosity carries out foaming for the makrolon of a certain particular range in the makrolon of the structural unit of alcohol, then can carry For the foam molded product that heat resistance, mechanical property are excellent, i.e. in the homopolymer of isobide, glass transition temperature (Tg) Its melt viscosity of high person is larger, poor fluidity, it is therefore desirable to foaming is carried out in high temperature, and this can cause resin that heat point occurs Solution, and the low person of glass transition temperature (Tg) in the homopolymer of isobide, melt viscosity are smaller, foaming is poor, because This can not carry out even foaming, etc..
[embodiment 2-1~2-4, comparative example 2-1~2-4]
< embodiments 2-1,2-2:The foaming > of Copolycarbonate (PC-1)
The poly- of Production Example 1 is put into the hopper of the MuCell injection moulding machines " J85AD-Mucell " of JSW companies manufacture Carbonic ester particle pressurizes as shown in table 3 to barrel inside (resin melting portion) in measurement process and imports (injection) physics hair Infusion (nitrogen or carbon dioxide), the PC-1 after melting is mixed with physical blowing agent.Then, to thick 1.5mm × wide The plate-like shape of 100mm × long 180mm mold injection, with filling complete almost simultaneously (filling complete before and after 0.1 second with It is interior), the movable platen of mold is only retreated and (move back core) given path increment (die sinking amount), the expansion of die cavity is carried out, is thus sent out Type is soaked, the state is kept to cool down 60 seconds, has obtained expanded moldings.In this case, " the mould of the calculating for expansion ratio The thickness of mold before chamber expansion " is 1.5mm.Since injection to filling complete required time be set as 1.0 seconds, The retrogressing required time of the movable platen of mold is set as 0.1 second.In addition, mold temperature is adjusted to 60 degree.
In addition, in table 3, expansion ratio is measured according to expansion ratio 2.
The results are shown in Table 3.
< embodiments 2-3,2-4:The foaming > of Copolycarbonate (PC-2)
In addition to the Copolycarbonate (PC-2) for having used Production Example 2, carried out in the same manner as embodiment 2-1,2-2 Foaming.
The results are shown in Table 3.It should be noted that in " foaming can be carried out " item in the embodiment 2-4 of table 3 " △ " generates molded product defect, rough surface although representing to be molded in a part for molded product.
< comparative examples 2-1,2-2:The foaming > of makrolon (PC-3)
In addition to the makrolon (PC-3) for having used Production Example 3, foamed in the same manner as embodiment 2-1,2-2 Shaping.
The results are shown in Table 3.
< comparative examples 2-3:The foaming > of makrolon S2000R (bisphenol-A class PC)
The Bisphenol-A based polycarbonate " S2000R " of Mitsubishi engineering Plastics Co., Ltd's manufacture and embodiment 2-1,2-2 is same Foaming has been carried out sample.Obtained formed body be particularly molten resin flow into downstream side end, almost whole It is found that supposition is due to deaerate and defect, the rough surface of the resin of generation on a formed body, not resistance to practicality.
The results are shown in Table 3.
< comparative examples 2-4:The foaming > of makrolon 7022IR (bisphenol-A class PC)
The Bisphenol-A based polycarbonate " 7022IR " of Mitsubishi engineering Plastics Co., Ltd's manufacture and embodiment 2-1,2-2 is same Foaming has been carried out sample.Obtained formed body be particularly molten resin flow into downstream side end, almost whole It is found that supposition is due to deaerate and defect, the rough surface of the resin of generation on a formed body, not resistance to practicality.
The results are shown in Table 3.
The evaluation criteria of " foaming can be carried out "
○:There is no molded product defect and rough surface, can be molded.
△:Although can be molded, molded product defect, rough surface are generated in a part for molded product.
×:Molded product defect, rough surface are generated on molded product, it is impossible to be molded.
< embodiments 3-1,3-2:Foaming (moving back core method) > of Copolycarbonate (PC-1)
The poly- of Production Example 1 is put into the hopper of the MuCell injection moulding machines " J85AD-Mucell " of JSW companies manufacture Carbonic ester particle pressurizes as shown in table 4 to barrel inside (resin melting portion) in measurement process and imports (injection) physics hair Infusion (nitrogen or carbon dioxide), the PC-1 after melting is mixed with physical blowing agent.In all embodiments, comparative example In, the path increment of metering reaches when can be set to that and being injected to the mold of the plate-like shape of thick 1.5mm × wide 100mm × long 180mm To the value injected entirely.Then, injected to the mold of the plate-like shape of thick 1.5mm × wide 100mm × long 180mm, with having filled Into almost (filling simultaneously before and after completing within 0.1 second), the movable platen of mold is only retreated and (move back core) given path increment and (is opened Modulus), the expansion of die cavity is carried out, thus carries out foaming, the state is kept to cool down 60 seconds, has obtained expanded moldings. In this case, " thickness of the mold before die cavity expansion " for the calculating of expansion ratio is 1.5mm.To filling out since injection Charge into the required time be set as 1.0 seconds, the retrogressing required time of the movable platen of mold be set as 0.1 second. In addition, mold temperature is adjusted to 60 degree.
The results are shown in Table 4.It should be noted that in core method is moved back, the mold thickness in table refers to " before die cavity expansion Mold thickness ".
In addition, in table 4, expansion ratio is measured according to expansion ratio 3.
< embodiments 3-3,3-4:Foaming (moving back core method) > of Copolycarbonate (PC-2)
In addition to the Copolycarbonate (PC-2) for having used Production Example 2, carried out in the same manner as embodiment 3-1,3-2 Foaming.
The results are shown in Table 4.It should be noted that in " foaming can be carried out " item in the embodiment 3-4 of table 4 " △ " generates molded product defect, rough surface although representing to be molded in a part for molded product.
< comparative examples 3-1,3-2:Foaming (moving back core method) > of makrolon (PC-3)
In addition to the makrolon (PC-3) for having used Production Example 3, carried out respectively in the same manner as embodiment 3-1,3-2 Foaming.
The results are shown in Table 4.
< comparative examples 3-3:Foaming (moving back core method) > of makrolon S2000R (bisphenol-A class PC)
The Bisphenol-A based polycarbonate " S2000R " of Mitsubishi engineering Plastics Co., Ltd's manufacture and embodiment 3-1,3-2 is same Foaming has been carried out sample.Obtained formed body be particularly molten resin flow into downstream side end, almost whole It is found that supposition is due to deaerate and defect, the rough surface of the resin of generation on a formed body, not resistance to practicality.
The results are shown in Table 4.
< comparative examples 3-4:Foaming (moving back core method) > of makrolon 7022IR (bisphenol-A class PC)
The Bisphenol-A based polycarbonate " 7022IR " of Mitsubishi engineering Plastics Co., Ltd's manufacture and embodiment 3-1,3-2 is same Foaming has been carried out sample.Obtained formed body be particularly molten resin flow into downstream side end, almost whole It is found that supposition is due to deaerate and defect, the rough surface of the resin of generation on a formed body, not resistance to practicality.
The results are shown in Table 4.
< embodiments 3-5,3-6:Foaming (short injection) > of Copolycarbonate (PC-1)
The poly- of Production Example 1 is put into the hopper of the MuCell injection moulding machines " J85AD-Mucell " of JSW companies manufacture Carbonic ester particle pressurizes as shown in table 4 to barrel inside (resin melting portion) in measurement process and imports (injection) physics hair Infusion (nitrogen or carbon dioxide), the PC-1 after melting is mixed with physical blowing agent.Then, to the thickness shown in table 4 The mold injection of the plate-like shape of × wide 100mm × long 180mm, keeps the state to cool down 60 seconds, has obtained expanded moldings. This be based in mould residual be not filled by portion carry out it is short injection and using foaming agent foaming generate expansive force filling do not fill out Portion is filled to carry out the foaming of molding method (short injection) progress.In this case, used in the calculating of expansion ratio " thickness for the mold that can be injected entirely " is 1.5mm.It is set as 1.0 seconds to the filling completion required time since injection Clock.In addition, mold temperature is adjusted to 60 degree.
The results are shown in Table 4.It should be noted that in " foaming can be carried out " item in the embodiment 3-6 of table 4 "×" expression can carry out foaming, but the loading in the underfill portion as caused by the expansive force of the foaming generation of foaming agent is not Foot, the molten resin of resin underfill to expanded moldings flow into the end in downstream side.
< embodiments 3-7,3-8:Foaming (short injection) > of Copolycarbonate (PC-2)
In addition to the Copolycarbonate (PC-2) for having used Production Example 2, respectively in the same manner as embodiment 3-5,3-6 Foaming is carried out.
The results are shown in Table 4.It should be noted that in " foaming can be carried out " item in the embodiment 3-8 of table 4 "×" expression can carry out foaming, but the loading in the underfill portion as caused by the expansive force of the foaming generation of foaming agent is not Foot, the molten resin of resin underfill to expanded moldings flow into the end in downstream side.
The evaluation criteria of " foaming can be carried out "
○:There is no molded product defect and rough surface, can be molded.
△:Although can be molded, molded product defect, rough surface are generated in a part for molded product.
×:Molded product defect, rough surface are generated on molded product, it is impossible to be molded.
The present invention is described in detail with reference to specific embodiment, but those skilled in the art should understand that It is that, in the case where not departing from the intent and scope of the present invention, various changes and amendment can be made.The application is based on 2011 The Japan to file an application in Japanese patent application (Patent 2011-189681) that August is filed an application on the 31st, on October 26th, 2011 is specially The Japanese patent application (Patent 2011-236746) that profit application (Patent 2011-235371), on October 28th, 2011 file an application And complete, in this application entire contents are introduced as reference.
Industrial applicibility
It is not particularly limited, can added as the industrial materials of wide range of areas using field for formed body of the invention To utilize.The present invention formed body due to light weight, impact resistance it is excellent, can particularly suitable for structural elements, be packed for Material, container, padded coaming, electric and electronic material, automobile component etc..

Claims (14)

1. a kind of expanded moldings, it includes Copolycarbonate, and glass transition temperature Tg is less than 145 DEG C, described poly- Carbonate copolymer has the structural unit of the dihydroxy compounds represented from following formula (1) and from other dihydroxy chemical combination The structural unit of object,
Wherein, the structural unit from other dihydroxy compounds is selected from least one of following structural units structure list Member:
The structural unit of the dihydroxy compounds represented from following formula (2),
HO-R1-OH (2)
In formula (2), R1Represent the substituted or unsubstituted ring alkylidene of carbon number 4~20;
The structural unit of the dihydroxy compounds represented from following formula (3),
HO-CH2-R2-CH2-OH (3)
In formula (3), R2Represent the substituted or unsubstituted ring alkylidene of carbon number 4~20;
The structural unit of the dihydroxy compounds represented from following formula (4),
H-(O-R3)p-OH (4)
In formula (4), R3Represent the substituted or unsubstituted alkylidene of carbon number 2~10, p is 2~50 integer;And
The structural unit of the dihydroxy compounds represented from following formula (5),
HO-R4-OH (5)
In formula (5), R4Represent carbon number 2~20 substituted or unsubstituted alkylidene or it is substituted or unsubstituted have contracting The group of aldehyde ring.
2. expanded moldings according to claim 1, wherein, the Izod impact strength of the Copolycarbonate is 30J/m2More than.
3. expanded moldings according to claim 1, wherein, it all is from compared with contained in Copolycarbonate The structural unit of dihydroxy compounds, the ratio of the structural unit of the dihydroxy compounds represented from formula (1) is 30 moles of % Above and 99 moles of below %.
4. expanded moldings according to claim 2, wherein, it all is from compared with contained in Copolycarbonate The structural unit of dihydroxy compounds, the ratio of the structural unit of the dihydroxy compounds represented from formula (1) is 30 moles of % Above and 99 moles of below %.
5. expanded moldings according to any one of claims 1 to 4, wherein, the resin combination meets following property Shape (1),
(1) carbon dioxide at 200 DEG C is 2.5 × 10 compared with the Henry's constant of resin combination-3~4.0 × 10-3G (two Carbonoxide)/g (resin combination) MPa resin combination.
6. expanded moldings according to claim 1, wherein, foaming agent is inorganic gas.
7. expanded moldings according to claim 6, wherein, inorganic gas is nitrogen or carbon dioxide.
8. according to the expanded moldings any one of claim 1,6~7, wherein, the cavity volume phase after die cavity expansion It is the scope more than 1.1 times and less than 20 times that cavity volume when completing is filled for resin combination.
9. a kind of manufacturing method of expanded moldings, this method include:
Compared with 100 mass parts of Copolycarbonate, using more than 0.1 mass parts and 20 foaming agents below mass part, lead to It crosses and carries out foaming with the foam-injection of die cavity expansion, so as to form expanded moldings,
The expanded moldings include Copolycarbonate, and glass transition temperature Tg is less than 145 DEG C, the makrolon Copolymer has the structural unit of the dihydroxy compounds represented from following formula (1) and the knot from other dihydroxy compounds Structure unit,
Wherein, the structural unit from other dihydroxy compounds is selected from least one of following structural units structure list Member:
The structural unit of the dihydroxy compounds represented from following formula (2),
HO-R1-OH (2)
In formula (2), R1Represent the substituted or unsubstituted ring alkylidene of carbon number 4~20;
The structural unit of the dihydroxy compounds represented from following formula (3),
HO-CH2-R2-CH2-OH (3)
In formula (3), R2Represent the substituted or unsubstituted ring alkylidene of carbon number 4~20;
The structural unit of the dihydroxy compounds represented from following formula (4),
H-(O-R3)p-OH (4)
In formula (4), R3Represent the substituted or unsubstituted alkylidene of carbon number 2~10, p is 2~50 integer;And
The structural unit of the dihydroxy compounds represented from following formula (5),
HO-R4-OH (5)
In formula (5), R4Represent carbon number 2~20 substituted or unsubstituted alkylidene or it is substituted or unsubstituted have contracting The group of aldehyde ring.
10. the manufacturing method of expanded moldings according to claim 9, wherein, compared with institute in Copolycarbonate What is contained all is from the structural unit of dihydroxy compounds, the ratio of the structural unit of the dihydroxy compounds represented from formula (1) Example is 30 moles of more than % and 99 mole of below %.
11. the manufacturing method of the expanded moldings according to claim 9 or 10, wherein, under the resin combination meets Character (1) is stated,
(1) carbon dioxide at 200 DEG C is 2.5 × 10 compared with the Henry's constant of resin combination-3~4.0 × 10-3G (two Carbonoxide)/g (resin combination) MPa resin combination.
12. the manufacturing method of expanded moldings according to claim 9, wherein, foaming agent is inorganic gas.
13. the manufacturing method of expanded moldings according to claim 12, wherein, inorganic gas is nitrogen or carbon dioxide Gas.
14. the manufacturing method of the expanded moldings according to any one of claim 9,12~13, wherein, after die cavity expansion Cavity volume compared with resin combination fill complete when cavity volume be more than 1.1 times and less than 20 times scope.
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